Dyestuffs containing metals and process of making same



Patented June' 29, 1926.

UNITED STATES PATENT OFFICE.

FRITZ STRAUB, OI BASEL, AND HERMANN SCHNEIDEB OF BIEHEN,-NEAR BASEL,

SWITZERLAND, ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OI!

BASEL, SWITZERLAND.

DYESTUFFS CONTAINING METALS AND PROCESS OF MAKING SAME.

Rb Drawing. Application filed April 7, 1925, Serial No, 21,439, and in Switzerland April 20, 1924.

corresponding with the general formula: on

wherein the naphthalene nucleus contains at least one more substituent and in which 1 It stands for an aromatic'nucleus not carrying any carboxyl-group and containing at the most'one nitro-group but carrying a hydroxy-group in ortho position to. the azo bridge, with agents yielding metals, such 7 as copper or chromium compounds. The azo-dyestufi's containing metals thus obtained form dark powders, dissolving in water with red to blue coloration yielding on wool, when dyed in an acid bath, fast violet to blue and dark green tints.

Ema mple 1.

14,35 parts of 4-chloro-2-amino-1-hydroxybenzene are diazotized as usual and added to a solution of 30,3 parts of l-hydroxynaphthalene 8 sulphamide-fl-sulfomc acid, 10 parts of caustic soda and 25 parts of sodium carbonate in 200 parts of water.

The mixture is stirred at 510 C. until the diazo-compound has disappeared whereupon the new dycstufi is isolated by adding common salt. The new dyestufi corresponding with the formula:

OH SOINHI l S01E- forms in a dry state a blackish powder, dis

solving in dilute acetic acid solution and in dilute caustic soda solution with bluish-red, in dilute sodium carbonate with Bordeauxred, in concentrated sulfuric acid with brownish Bordeaux-red colorations, dyeing W001 111 an acetic acid bath brown-red tints, which when afterchromed become violet, aftercoppered red-violet. The isomeric dyestufis from l-hydroxynaphthalene-8-sulfamide-3-sulfonic acid and the dyestufi from 1-hydroxynaphthalene-8-sulfamide-4-sulfon- 1c acid and diazotized l-nitro-aminoph'ehol behave in an analogous manner. The dyestufi' from diazotized 1-amino-2-hydroxynaphthalene-4-sulfonic acid and 1hydroxyna hthalene-8-sulfamide-4-sulfonic acid disso vesin acidulated water with bluish-red, in dilute carbonate of soda solution with greenblue, in concentrated sulfuric acid with blue coloration. Its dyeings on wool, when after coppered, are violet, when after chromed dark blue; the isomeric dyestufl from l-hydroxynaphthalene 8 sulfamide 3 sulfonic acid dissolves in sodium carbonate solution with violet, inv concentrated sulfuric acid with violet coloration and shows similar properties.

Example 2.

14,3 parts of 4-chloro-2-amino-1-hydroxybenzene are diazotized in the usual manner and are introduced at 5--10-C. into a solution of 30,2 parts of l-hydroxynaphthalene- 3,8-disulfamide, 27 parts of caustic soda solution of 30 er cent strength and 10 parts of sodium car onate in parts of water. The mixture is stirred at 10 C. until cou- 90 pling is complete, then diluted with 150 parts of water and poured into 140 parts of a solution of hydrochloric acid of 15 per cent strength. The dyestufi is salted out. It forms a dark powder, dissolving in dilute acetic acid solution and in dilute caustic soda solution with blue-red, in dilute sodium carbonate solution with violet, in concentrated sulfuric acid with black-violet coloration, dyeing wool in an acetic acid bath redviolet tints which become pure marine-blue and of good fastness when after chromed, and violet when after coppered.

Example 3.

1 Into a solution of 56 parts of caustic otash in 48 parts of water are introduce at 50 C. 30,2 parts of l-hydroxynaphthalene- 4,8-disulfamide. After stirring for some time there is added at -50" C. the diazocompound from 31,8 parts of l-hydroxynaphthalene-8-s/ulfamide'2-aminoi-sulfonic acid in the form of a paste of 49 per cent strength and at the last-named temperature. WVhen coupling is complete the mass is diluted with parts of cold water and the whole is poured into 200 parts of hydrochloric acid of 21 per cent strength, while stirring well; the new dye-stufl is then salted out. It forms a blackish powder dissolving in water acidulated with acetic acid, with bluish-red. in dilute caustic soda with red-violet, in dilute sodium carbonate solution with bluish-violet, in concentrated sulfuric acid with cyaneous coloration, dyeing wool in an acetic acid bath violet tints which pass to a pure greenish blue 'of excellent fastness when after chromed and to blueviolet when after coppered.

Example 4.

18,5 parts of et-chloro-1-hydroxynaphthalene-S-sulfamide are introduced at 20 into a solution containing 27 parts of caustic potash and 30 parts of water and stirred at this temperature until the corresponding potassium salt has been formed. The mixture is then cooled at 10 and treated with 13,6 parts of the sodium salt of the diazo-compound of 1-amino-2-hydroxynaphthalene-4- sulfonic acid (in form of a paste of 50 per cent strength). Stirring is continued until the coupling is achieved, and the temperature is allowed to rise to 20; the mixture is diluted with water, neutralized with dilute hydrochloric acid and the dyestufi' thus obtained salted out. It forms a black powder, dissolving in water with Bordeaux, in caustic soda solution with red-violet, in concentrated sulfuric acid with blue coloration.

- The dyestuffdyes wool in an acid bath dull Bordeaux tints which become greenish-blue when after chromed. If the diazo-compound of the l-amino-2-hydroxynaphthalenei-sulfuric acid is substfiuted by the corresponding nitro-diazo-derivativ, a dyestufl forming a dark powder is obtained dissolving in water with red-violet in dilute caustic soda solution with red-brown, in concentrated sulfuric acid with blue coloration and dyeing wool from an acid bath dull violet-Bordeaux tints, becoming black-green when after chromed.

The et-chloro-1-hydroxynaphthalene-8-sulfamide forms a yellowish powder. It is obtained by causing to react ammonia on 4- chloro-1,8-naphthsultone.

Example 5.

42,3 parts of the dyestufi' from 4-chloro-2- amino-l-hydroxybenzene and l-hydroxynaphthalene-8-sulfamide-4-sulfonic acid are dissolved in 800 parts of boiling water. To

. the whole Cr(OH) is dissolved.

the solution is added a solution of chromium formate corresponding with 16 parts of Cr O and the whole is boiled for a long time in the reflux apparatus. By evaporating and salting out the new chromium compound is obtained. It forms a blackish powder, dissolving in water with blue coloration and red appearance, in dilute caustic soda solution with red-vio'let coloration, dyeing wool in an acid bath violet tints with excellent properties of fastness. The isomeric dyestuff from 1-hydroxynaphthalene-8-sulfamidei-sulfonic acid shows similar properties; the dyestuii from diazotized t-nitroaminophenol yields a somewhat redder tint.

Erample 6.

Into 5% parts of an aqueous paste of chromium hydroxide containing 16,2 per cent of Cr there are introduced in small portions 60 parts of solid caustic potash until To this solution are then added 57,3 parts of the dyestufi from 1-hydroxynaphthalene-S-suliamidel-sultonic acid and diazotized 1- amino-2 hydroxynaphthalenet-sulfonic acid and the mixture heated at 80 C. until the whole chromium has been absorbed by the dyestufl'. The reaction mixture is then diluted with water, neutralized with mineral acid and the dyestutt thus obtained salted out with common salt. It forms a dark powder, dissolving in water with blue, in dilute caustic soda. solution with violet coloration and dyeing wool in an acid bath blue fast tints. The chromium compounds of the dyestuffs described in the examples Nos. 2 and 3 yield on wool blue tints remarkable by their purity.

5 parts of the dyestuti from i-chloro-l liydroxynaphthalcnc-8-sulfauiide and l.- amino-2-hydroxynaphthaleneA-sultonic acid are dissolved in 100 parts ot boiling water, treated with a chromium forinatc solution corresponding with 2,5 parts of 01- 0., and boiled for some time in a reflux apparatus. The chromiuni-compound is then obtained by evaporating and alting out. It forms a blackish powder, dissolving in water with greenish-blue. in caustic sodav solution with blue violet. in concentrated sulfuric acid with bluish-green coloration and dyeingwool in a sulfuric acid bath greenish-blue tints. The chromium compound of the dyestutf from 4-chloro-1hydroxynaphthalene- S-sulfamide and the nitrated dia; co-con|- pound of l-amino-2-hydroxynaphthalone-t sulfonic acid for-ms a blackish powder d ssolving in water with bluish-green. in concentrated sulfuric acid with blackish-blue. in concentrated caustic soda solution with riolet coloration and dyeing wool in an acid bath dark green tints.

Example 8.

57,3 parts of the dyes'tufi from l-hydroxynaphthalene-S-sulfamide-3-sulfonic acid and added a concentrated solution of 27 parts of copper sulfate and the mixture is warmed parts of sodium acetate and the new dyestufli' is salted out. The new dyestufl forms a dark powder,- dissolving in water and dilute caustic soda solutionredwiolet tints, and yielding on wool in an acid bath fast violet'tints. The copper-compounds of the other dye- I than one nitro group fland treating the dyestufis.thus obtained with agents yieldingchromium.

6. The herein described process for the manufacture of new dyestufis-by combining the substitution products of the l-hydroxynaphthalene-S-sulfamide of which the substituents are other sulfamide groups with ohydroxy-diazo-compounds' not carr in an ior a short time. There are then added 15 y g y carboxyl group and containing not more than one nitro group and treating the" -dyestufls thus obtained with agents yielding chromium.

7. As new products the metal-compounds of the dyestuffs of the general formula HzN'-SO1 OH stuffs described in the first examples yield also red-violet to blue-violet tints on wool.

What we claim is: 1. The hereindescribed process for the manufacture of new dyestuffs by combining the substitution products of the l-hydroxynaphthalene-EB-sulfamide with o-hydroxydiazo-compounds not carrying anycarboxyl group and containing not more than one nitro group and treating the dyestuffs thus obtained with agents yielding metals.

2. The herein described rocess for the manufacture of new dyestu s by combining i the substitution products of the l-hydroxynaphthalene-8-sulfamide of which the substituents correspond with the general formula '-SO X, (X=OH or N11,) with o-hydroxy-diazo-compounds not carrying any carboxyl group and containing not more than one nitro group and treating the.dye-

stuifs thus obtained with agents yielding metals.

3. The herein described rocess for the manufacture of new dyestu s by combining the substitution products of the 1-h droxynaphthalene-S-sulfamid of which t e substituents are other sulfamide groups with o- 'hydroXy-diazo-compounds not carrying any carboxyl group and containing not more than one nitro group and treating the dyestuffs thus' obtained with agents yielding metals.

4. The herein described rocess for the manufacture of new dyestu s by combining y the substitution products of the l-hy- 'droxyna phthalene-8-sulfamide with o-hy droxy-dia-zo-compounds not carrying any carboxyl group and containin not more than one nitro grou and treatnig the dyestuifs thus obtaine with agents yielding chromium. I

5. The herein described rocess for the manufacture of new dyestu s by combining wherein the naphthalene nucleus contains at least one more substituent, R standing for an aromatic nucleus carrying a hydroxyl group in ortho position to the azo-bridge, not carrying any carboxyl group and containing at the most one nitro group-,which dyestufis form dark powders, dissolving in""- wherein the naphthalene nucleus carries one more substituent corresponding with the gen eral formula SO X (X=OH or NH,), R standing for an aromatic nucleus carrying a hydroxyl group in ortho position to the ambridge, not carrying any carboxyl group and containing at the most one nitro up, which dyestufis form dark powders, d1ssolving in water with red to blue coloration and ieldin on wool when dyed in an acid bath fastre -violet toblue and dark green tints. 9. As new roduct the metal compounds of the dyestu s,,of the general formula ran-so,

wherein the naphthalene nucleus carries one more so nn group, R standing for an aromatic nucleus carrying a hydroxyl group in ortho position to the azo-bridge, not car-.

rying any carboxyl group and containin at the most one nitro group, which dyestu s form dark powders, dissolving in water with red to blue coloration and yielding on wool when dyed in an acid bath fast red-violet to blue and dark green tints.

10. As new products the chromium compounds of the dyestuffs corresponding with the general formula:

wherein the naphthalene nucleus contains at least one more substit-u'ent, R standing for an aromatic nucleus carrying a hydroXyl group in ortho position to the aZo-bridge, not carrying any carboxyl group and containing at the most one nitro group, which dyestuffs form dark powders, dissolving in wherein the naphthalene nucleus carries one more substituent corresponding with the eneral formula SO X (X=OH or NH it standing for an aromatic nucleus carrying a hydroxyl group in ortho position to the azo-bridge, not carrying any carboxyl group and containin at the most one nitro roup, which dyestuffs form dark powders, dissolving in water with red-violet to blue, in dilute caustic soda solution with red-violet colorations and yielding on wool, when dyed in an acid bath, fast violet to blue and dark green tints.

12. As new products the chromium com; pounds of the dyestuffs corresponding with the general formula:

inn-02s 011 wherein the naphthalene nucleus carries one more SO 'NH group, R standing for an aromatic nucleus carrying a hydroXyl group in ortho position to the azo-bridge,.not carrying any carboxyl group and containing at the most one nitro group, which dyestuffs form dark powders, dissolving in water with red violet to blue, in dilute caustic soda solution with red-violet colorations and yielding on wool, when dyed in an acid bath, fast violet to blue and dark-green tints.

13. Material dyed with the dyestufls claim 7.

14:. Material dyed claim 8.

15. Material dyed claim 9.

16. Material dyed claim 10.

17. Material dyed claim 11.

with the dyestufls with the dyestuffs with the dyestuffs with the dyestuffs of 18. Material dyed with the dyestuffs of I FRITZ STRAUB. HERMANN SCHNEIDER. 

